Green-black sulfur dye.



Units Ares PAUL JULIUS, or LUD'WIe'sHAFEN, GERlilANY, ASSIGNOR TO THE BADIsoHn ANILIN AND SODA FABRI'K, OF SAME PLACE.

= GREENPBFLACK SULFUR DIYE.

SBEOIFEGATION forming part of Letters Patent 1N0; 648,754, dated may 1, i900.

Applicatio'n filed are, e, 1 00. Serial No. 4,263. no specimens.)

To aZZ whom it may concern: T

Be it known that 1, PAUL JULIUS, doctor 4 philosophy, asubject of the Emperor of Austrier-Hungary, residing at Ludwigshafen-onand this, when treated in the manner to be described with sulfur and sodium sulfid, yields the coloring-matter I desireto claim..

the-Rhine, in the Kingdom of Bavaria and Empire of Germany, have invented new and useful Imprdvements in Green-Black Dyestn ffs, of which the following is a specification. My invention relates to the manufacture of a new green-black coloring-matter which dyes cotton without the aid of a mordant.

This dyestuli is'obtained-bytreating a certain meta-phenylendiamin derivative with sulfur and sodium sulfid. The said metaphenylendiamin derivative results from the condensation in aqueous solution of one mole cnle of symmetrical dinitro-meta-di-chlorbenzone and two molecules of pa'ra-amido-phenolortho-sulfoacid in the presence of a body that will bind hydrochloric acid, such as sodium carbonate or acetate. In this'way dinitrodi para-hydroxy-di p'henyl-meta phenylendiamin-di sulfoacid is obtained which, j u'dging' from the manner of its formation, has the following constitutional formula:

so,u

. The following example'will serve to further illustrate the manner in which my invention.

can be carried into practical eiiect and my new coloring-matter obtained. The parts areby weight.

Production pzf green-black coloring-matter 59 from denit'ro- 11 -pam hyd'ronzy d1; qilie nylmeta-phenyZendiamtn-di-subbacid. Prepare the required initial material by heating to boiling in a reflux apparatus a mixture of one molecular proportion of dinitro-di-ohlorbenzone and two molecular proportions of paraamido-phenol-ortho-sulfoacid, the latter dissolved in water, and sufficientsodium acetate to bind the hydrochloric acid formed during four hours or until the dinitro-di-chlorbenzone has practically disappeared. Allow the liquid to 6001- and isolate the reaction product in any well-known manner. Mix together twenty (20) parts of the dinitro-di-para-hydroxy-di-phenyl-meta-phenylendiamin-di-sulfoacid thus obtained with forty (40) parts of sulfur, one hundred and twenty (120) parts of or'ystallizedsodium sulfid, and five (5) parts of water in an iron vessel. Gradually heat the mixture to'about 140 centigrade while. stirring and maintain at this temperature until the melt'h-as become quite dry. When cool, powderit up. In this condition it can be directly used for dyeingpurposes, or it may be dissolved in a little Water and the coloring-matter salted out with common salt. In this case it'is' necessary, when dyeing, to

' add soda, common salt, and sodium sulfid to the dyeing-bath in order to obtain the best re- 8o sults.

My new coloring-matter is readily soluble in water, its aqueous solution being green. Acids added to this solution produce a brown precipitate, which is redissolved by alkalies withia green color, 'It dyes .unniordanted cotton a green black, which is exceedingly fast to soap, light, and acids. It is but little alteredinfastness or shade by subsequent treatmontwith chromates', copper salts, and 0 the like. v

Now what I claim is The new coloring-matter which can be ob taincd from dinit'ro dipara hydroxy di sulfur and sodium sulfid, whose solution in water is of a green color, dyeing ufiinordanted i cotton a green black, which is not materially the reaction. Continue the heating for about 66 phenyl m etaphenylendiamin di sulfoacid, 9'5

altered in shade or fastness by treatmentwith my hand in the presence of two subscribing chromates and copper salts, and in .which 30- witnesses. iution a brown precipitate is formed on the i v w addition of hydrochloric acid, the said pree PAL L U 5 eipitatc redissolving in aik'aiies with a green Witnesses: i. color substantially as described. JACOB ADRIAN, v

in testimony whereof I have hereunto set ERNEST I EHRHARD'P. 

